2,2,5,5-tetraperhaloalkyl-4,4-dialkoxy substituted-1,3-dioxolane



United States Patent 3,467,674 2,2,5,5-TETRAPERHALOALKYL-4,4-DIALKOXY SUBSTITUTED-1,3-DIOXOLANE Robert A. Braun, N ewark, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 439,452, Mar. 12, 1965, which is a continuation-in-part of application Ser. No. 325,468, Nov. 21, 1963. This application. May 24, 1967, Ser; No. 640,802

Int. Cl. C07d 13/04, 15/04, 17/04 US. Cl. 260-3409 4 Claims ABSTRACT OF THE DISCLOSURE Compounds having the formula R and R can be alkyl or substituted alkyl, alkenyl, cycloalkyl, phenyl or substituted phenyl,

R and R can be bridged by various divalent radicals,

R, can be a perfluoroalkyl or monochloroperfiuoroalkyl,

and

R, can be perfluoroalkyl.

CROSS-REFERENCES To RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 439,452, filed Mar. 12, 1965, which in .turn is a continuation-in-part of application Ser. No. 325,468, filed Nov. 21, 1963 both now abandoned.

SUMMARY oF THE, INVENTION This invention relates to fluoro-substituted dioxolanes. It is more particularly directed to compounds represented by the structural formula R and R can be alkyl of 1 through 18 carbon atoms; alkyl of 1 through 18 carbon atoms substituted with chlorine or fluorine; alkenyl of 2 through 6 carbon atoms; cycloalkyl of 3 through 7 carbon atoms; phenyl; phenyl substituted with chlorine, bromine, fluorine,

Patented Sept. 16, 1969 ice OCH alkyl of 1 through 5 carbon atoms or -NO R and R can be connected by GHQ-0 0 H? t where A can be hydrogen or alkyl of 1 through 5 carbon atoms, and Z can be alkyl of 1 through 17 carbon atoms or -CH OCH CH=CH 2)n-sor JH 2-a where X can be Cl, Br, -F, -CN, --COOR (R can be an alkyl radical of 1 through 5 carbon atoms), -0H, -OCH -CH=CH SH, -SCN, or

where R and R; can be alkyl of 1 through 5 carbon atoms, halo-substituted alkyl of 1 through 5 carbon atoms or phenyl, and can be connected by a (CHZ)Z-6 radical;

R can be perfluoroalkyl or monochloroperfluoroalkyl containing 1 through 5 carbon atoms; and R, can be perfluoroalkyl of 1 through 5 carbon atoms.

These properties make the compounds of the invention useful as dielectric, heat transfer and hydraulic fluids, and as buoyancy and damping fluids in measuring and recording instruments. Those compounds which are viscous liquids or low melting solids are also useful as extreme temperature bearing lubricants.

The compounds of the invention which bear polymerizable vinyl groups can be polymerized using conventional vinyl polymerization techniques. The resulting polymers, because of their high fluorine content, are useful as soil and water repelling agents and as film forming components in coating compositions which given highly durable finishes.

Preparation of the compounds The compounds of the invention can be prepared according to the following general equation:

where R R R and R are as described in Formula 1, R is lower alkyl and R and R can be joined by an alkylene bridge of 2 through 5 carbon atoms.

Stoichiometric quantities of the ortho ester and ketone reactant are placed in a sealed container, which is then heated to a temperature of from 50 to 175 C., for from 2 to hours, preferably 125 to 150 C. for from 6 to 8 hours. Generally speaking, one must use the lowest possible temperature to avoid rupturing the ring of the cyclic acetal product. In most cases, reaction temperatures up to about 150 C. will give high yields, but in some instances higher temperatures can be used.

The reaction mixture is then cooled to room temperature. The hemiketal by-product is removed under vacuum and can be collected in a vacuum trap for recovery of the ketone reactant. The compounds of the invention are left behind as residue.

DESCRIPTION OF THE PREFERRED EMBODIMENT The invention will be more easily practiced by referring to the following illustrative examples:

Example 1 A mixture of 15.9 parts of trimethyl orthoformate and 74.8 parts of hexafluoroacetone was heated at C. for six hours in a bomb. The resulting liquid product was fractionated to give 2,2,4,4-tetrakis-trifluoromethyl-5,5- dimethoxy-1,3-dioxolane, having a boiling point of 161/760 mm., a freezing point of 0 C. and the structural formula The product did not burn or support combustion. It was unreactive with the following at 25 C. and 100 C.: concentrated sulfuric acid, concentrated nitric acid, 50% sodium hydroxide, boron trifiuoride gas and 50% hydrochloric acid.

The orthoformates in the following list can be substituted, in the listed amounts, for the trimethylorthoformate used in Example 1 to give the corresponding compounds of the invention:

Ortholoi'mate Amount,

part Product 'Iri(2,2,2-trifluoroethyl) ortholormate Tri-eycloliexyl orthoforiuate Diplieuyl methyl orthoformate 46.5 FaC-CH20 CF:

Example 2 CzHsO CF CzHsO CF:

The reactants in the following list can be substituted, in the listed proportions, for the hexafluoroa'cetone or triethyl orthoformate used in Example 2, to produce the corresponding dioxolane products:

6 give 25.9 parts of 2,2,4,4-tetrakis-trifluoromethyl-S,S-di-namyl-oxy-l,3-dioxolane having a boiling point of 231 C. at 760 mm. of pressure, a freezing point of less than -50 C. and the structural formula Odi -Oh C F 0 CFs CF:

This dioxolane was stable in air at 231 C.

Example 4 A mixture of 66.5 grams of hexafiuoroacetone and 2- methoxy-l,3-dioxolane was heated in a stainless steel bomb at 150 C. for six hours.

The residue was fractionated to give a colorless, odorless oil having a boiling point of 176 C. at 760 mm. and a freezing point of 24 C. This product had the structure CF CFs Amount,

Reaetant parts Product Ohloropentafluoroacetouo 81 Tri-2-ethylhexyl orthoiormate Tristearyl orthoionnate 123 C1sH37-O CHEM-0 CF; C1

Triallyl ortholormate. CHFCH-CH -O CFa O CF: CFs

Example 3 A mixture of 25 parts of tri-n-amyl orthoformate an 45.5 parts of hexafiuoroacetone was heated at 15Q C. for eight hours in a bomb. The residue was fractiohated to The cyclic ortho ethers in the following list can be used,

d in the listed proportions, in place of the 1,3-dioxolane in Example 4, to give the corresponding compounds of the invention:

Amount, Cyclic Ortho Ether parts Product 2-methoxy-5,5-dimethyl-L3-dioxane. 32 H 0 CH2O Cyclic Ortho Ether Amount,

parts Product 2methoxy-l,2-methylone dioxybeuzene. 30. 4

0 F3 0/ I C I;

2-mothoxybutouediollorinul 2-etl10xy-4,5-tetramethylenc 1,3-dioxolano Zamothoxy-,5-bonzo-l,3-dloxano 2'methoxy-3,4,5,6-tetrafiuoro-1,2-uiethylene dioxybouzeue...

2-mctl10xy-5,5 bis(allyloxymcthyl) 1,3-di0xane CF; CFa

Example 5 A mixture of 100 parts of 2-ethoxy-4-chloromethyl-1,3- dioxolane and 100 parts of hexafluoroacetone was heated in a bomb at 150 C. for six hours. The crude product was fractionated to give a chloromethylspiro-dioxolane having the structure CF; OFs

This compound had a boiling point of 197 C. at 760 mm. of pressure and a freezing point of less than C.

Example 6 (1) R-Cl KCN R-CN R-Cl on (base) H2O R-OH (3) CH3 CH3 0 This methacrylate monomer can be used to prepare polymeric film-forming components for use in coating compositions and for soil and water repellant textile treatments by polymerizing it according to conventional techniques, in solution or emulsion, using free radical catalysts.

where R and R are hydrogen or alkyl of 1 to 5 carbon atoms or phenyl, or where R and R are connected by a Reactions of this type are discussed in greater detail in J. Gen. Chem., 32, 3189 (1962).

I claim: 1. A compound having the formula R 0 /R;

C Rio l I R| Rz R-l where R, and R are alkyl of 1 through 18 carbon atoms;

3,467,674 9 10 alkyl of 1 through 18 carbon atoms substituted with 4. A compound having the formula chlorine or fluorine; alkenyl of 2 through 6 carbon atoms; cycloalkyl of 3 through 7 carbon atoms; phenyl; phenyl substituted with chlorine, bromine, fluo- E3 rine, -OCH alkyl of 1 through carbon atoms or 5 R is pcrfluoroalkyl or monochloroperfluoroalkyl, both containing 1 through 5 carbon atoms; and

R is perfiuoroalkyl of 1 through 5 carbon atoms. CFQ CF; 2. A compound having the formula H300 O 0 References Cited 1 UNITED STATES PATENTS OQCF, 3,308,064 3/1967 Schlight et a1. 260340.9 X

3. A compound having the formula ALEX M AZEL Primary Examiner JAMES H. TURNIPSEED, Assistant Examiner CHa(CH2)a-CH:O 01 's us. 01. X.R. CH (CH ClI-I20 O O CFS 260-239, 294.7, 326.16, 338, 340.5

CzHli 

